Biodegradable sorbents

ABSTRACT

Disclosed is a sorbent that includes spent grain germ, seed meal, or a mixture thereof. The sorbent may be used to introduce a material into an environment. For instance, the sorbent may be used to introduce a control agent, such as an insecticide or larvicide, into an environment. The sorbent also may be used to remove an unwanted material from an environment. For instance, the sorbent may be used to sorb oil or a hazardous chemical that has been spilled. The disclosed sorbents are biodegradable over a wide range of environmental conditions.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

[0001] This application claims priority to prior application Ser. No.60/298,861, filed Jun. 15, 2001. The content of this application isincorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The invention relates to a grain based material useful as ageneral sorbent. In some embodiments, the invention relates to theintroduction of a material into an environment, the material beingsorbed within the sorbent. These embodiments are particularly applicableto the introduction of a control agent, such as a mosquito larvicide,into an environment. In other embodiments, the invention relates to theremoval of a material from an environment by sorbing the material withinthe sorbent.

BACKGROUND OF THE INVENTION

[0003] Many methods exist for removing an undesired material from anenvironment. For instance, numerous products are available commerciallyfor removing spilled liquids from a surface. Some such products are usedto remove oil from open water, such as when an oil spill has occurred.In this application, it is desirable to selectively remove oil fromwater. For such absorbents, efforts are sometimes made to increase theselectivity of oil over water.

[0004] Currently available products for spill control include clay,kaolin, illite, bentonite, diatomite, hectorite, montmorillonite,attapulgite, silica, silica sand, polypropylene, sodiumpolyacrylate/polyacrylamides, vermiculite, gypsum, limestone, metaloxides, asphalt, fiberglass, diatomaceous earth, perlite and othermaterials. Such materials, while satisfactory in function, suffer fromcertain drawbacks. Many such products contain silica, which poses ahazard to humans. In addition, most such materials are notbiodegradable, which is a factor that can limit the options for disposalof the used sorbent material.

[0005] There are also several organic spill control products describedin the art. Examples of such materials include natural fibers such asgrass, pre-cooked cereal kernels, sawdust, cellulose, and peat. U.S.Pat. No. 5,492,881 purports to describe a cellulose based sorbentsystem, where the cellulose has been treated with an additive to renderit both hydrophobic and oleophilic so it will selectively remove oilfrom water. U.S. Pat. No. 4,969,774 purports to describe the use ofpre-cooked and puffed cereals for oil removal. Another document, U.S.Pat. No. 5,399,350, purports to disclose a particulate milled seedmaterial in which the lipids have been removed through solventextraction and wherein the material is designed to remove and disperseoil from open water and solid surfaces. The composition is asolvent-extracted proteinaceous material derived from grain productshaving oil sorptive properties. Also, U.S. Pat. No. 5,492,881 purportsto describe the use of diatomaceous earth, clay, silica, corncob,peatmoss, perlite, polypropylene, sawdust, cellulose, polystyrene,vermiculite, peat and cork to absorb liquids. This composition is taughtas a general absorbent; in this document, it is stated that materialsthat absorb both water and oil are undesirable. U.S. Pat. No. 5,891,937purports to disclose the use of corn stalks, husks, cobs, and kernels ascarriers. U.S. Pat. No. 6,110,323 purports to disclose the use ofdelignified waste from hulls, straw, stover, and shells as a carrier.Other carriers are purportedly disclosed in U.S. Pat. Nos. 6,383,609 and6,391,120. Generally, other biodegradable materials such as peat moss,sawdust, hair, feathers, cotton, cork, starch, bagasse, seeds, seedhulls, and other seed components have also been proposed.

[0006] Many methods for introducing a material into an environment alsoare known. In many cases, it is desired to introduce the material in adelayed-release manner, by which is contemplated that at least some ofthe material is bound up with another material or otherwise is notimmediately available to function in the environment for its intendedpurpose. For instance, it is often desired to introduce a control agent,i.e., a material that limits the growth or spread of a living thing,into an environment. Known control agents, such as insecticides,larvicides, rodenticides, fungicides, and so forth may be oil-based orwater-based. It is desirable to provide a sorbent for such controlagents, and in particular, it is desirable to provide a sorbent thatallows delayed release of at least some control agents into anenvironment. Further, it is highly desirable to provide a sorbent thatis useful in sorbing both oil- and water-based control agents.

[0007] Typical control agents are provided in liquid or solid form.There are advantages and disadvantages to each product form. Liquidpesticides can be applied as a spray, which is advantages in somerespect. Drift control of the spray can be a challenge, however,especially in an aerial broadcast application. Solid pesticide productsare better at targeting an area for pest control, because there is lessdrift of the solid product. Pelleted or compacted compositions aretypically used in solid pesticide products. The majority of suchcomposition is composed of a carrier or absorbent material, and theactive ingredient is usually a small percentage (<10%) of the pelletweight. Another advantage of a solid control agent composition is thatthe weight of the composition allows penetration into vegetative areasthat are less accessible via a liquid spray. Heavier pellets often canpenetrate through a tree canopy, whereas liquid droplets would tend tocoat and contaminate the tree canopy.

[0008] One drawback to many known solid pesticides products is thatnon-biodegradable carriers often are used in such products. Thesecarriers can lead to contamination of the area of treatment. Inrecognition of this problem, numerous biodegradable carriers have beenprovided; examples include materials such as corncob, peanut hulls, andstarches. Many known biodegradable carriers are unsatisfactory. In manycases, the resulting composition does not perform as well as anon-biodegradable product. In addition, many biodegradable materialssuch as corncob, peanut hulls, and starches do not disperse easily whenin contact with water, leaving a contaminant residue. Corncob isespecially poor in this regard, because it has low density as well aspoor dispersibility in water. In addition, when a granular pesticidedoes not readily disintegrate in an aquatic environment, the activeingredient is not readily released and thus a less efficacious pestcontrol product with residual contaminant pesticide activity isprovided.

[0009] In the case of mosquito larvicides, such materials ordinarily arereleased into standing or slowly moving water to destroy larvae growingin the water. It is particularly preferred that the carrier shouldrelease at least a portion of the larvicide within the topmost two feetof water in a standing or slowly moving water column, where most or allof the larvae are found. It is further preferred that the larvae in thewater column be destroyed within 24 hours, and preferably within 8 hoursof treatment. Although the prior art has provided numerous carriers forcontrol agents, not all carriers allow for the preparation of a controlagent composition that meets these preferred criteria.

[0010] In a first preferred embodiment of the invention, it is a generalobject to provide a sorbent that is useful in conjunction with theintroduction of a material into an environment. In a second preferredembodiment of the invention, it is a general object to provide a sorbentthat is useful in conjunction with the removal of a material from anenvironment, the material being removed by sorption of the material intothe sorbent and removal of the sorbed composition thus formed from theenvironment.

THE INVENTION

[0011] The invention provides a number of embodiments in which thesorbing properties of spent grain germ and seed meal are utilized. Theseorganic, naturally derived sorbents, alone or in combination, can beused to introduce material into an environment, or to remove materialfrom an environment. When such sorbent is used to introduce a materialinto an environment, the environment preferably is one in which thesorbent will biodegrade. In such instances, delayed release of thesorbed material into the environment often is possible. When the sorbentis used to remove material from an environment, the sorbed materialcomposition can be allowed to biodegrade prior to ultimate disposal ofthe composition. Many of the disclosures in the prior art fail toaddress the fate of the sorbed composition formed upon removing amaterial from an environment. Generally, the volume of sorbentintroduced into the environment is much greater than the volume of theliquid to be removed from the environment. Where the removed material isor contains a hazardous compound, the relatively large quantity ofsorbent having the material sorbed therewithin must also be treated as ahazardous material, which can increase the ultimate disposal costconsiderably. The sorbents useful in conjunction with the presentinvention can be biodegraded, thereby reducing the total volume ofmaterial that must be treated as hazardous.

[0012] In accordance with one embodiment of the invention, a controlagent composition is provided. The composition includes a sorbent, thesorbent being selected from the group consisting of spent grain germ,seed meal, and mixtures thereof, and a control agent sorbed within thesorbent. Most preferably, the composition is in the form of discreteplural pellets, by which is contemplated the product of a pelletizingoperation in a pellet mill.

[0013] In accordance with another embodiment of the invention, a methodfor limiting the growth of an undesired pest in an environment isprovided. The method includes selecting a control agent for the pest,and introducing into the environment an amount of a control agentcomposition effective to limit the growth of the pest. The control agentcomposition includes a sorbent and control agent as describedhereinabove.

[0014] In accordance with another embodiment of the invention, a methodfor introducing a material into an environment is provided. A materialfor which delayed release into the environment is desirable is selected.Subsequently, a granular material composition that includes the selectedmaterial sorbed within a sorbent, the sorbent being spent grain germ,seed meal, or a mixture thereof, is introduced into the environment. Thetiming of the release of the material into the environment can becontrolled to an extent by adjusting the integrity of the granules,whereby more durable granules generally will release the sorbed materialmore slowly than less durable granules.

[0015] In accordance with another embodiment of the invention, a methodfor removing an unwanted material present in an environment is provided.The method includes selecting a sorbent for the material, introducinginto the environment an amount of the sorbent effective to sorb at leasta portion of the material, allowing at least some of the material tobecome sorbed to thereby formed a sorbed composition, and removing atleast a portion of the sorbed composition from the environment. Thesorbed material may be a combustible material, and, in accordance withone embodiment of the invention, a method for generating heat isprovided, the method including providing a combustible materialcomposition and oxidizing the combustible material composition. Thecombustible material composition includes a sorbent and a combustiblematerial sorbed within the sorbent. Preferably, the combustible materialis present in an amount of at least 5% by weight of the composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The invention contemplates the use of a sorbent, by which iscontemplated a material that absorbs and/or adsorbs another material.Generally, absorption is a term used in the art to refer to thepenetration of one substance into the inner structure of anothersubstance, whereas the term adsorption refer to adherence of atoms,ions, or molecules onto the surface of another material. It is believedthat one or both phenomena occur in accordance with the variousembodiments of the invention, but it is contemplated that the materialmay serve as a sorbent even if only one of the two phenomena is present.By “sorbed within” is herein contemplated the sorption of a material inor on the sorbent.

[0017] The sorbent used in conjunction with the invention preferably isspent germ, which is a germ from which oil has been expelled, forinstance, by pressing or extraction with an extracting liquid such ashexane or water. Spent grain germ material has numerous advantages, inthat it is derived from natural, renewable resources, is biodegradableand safely incinerable, is nontoxic and safe for the environment, and iseconomical to produce and use. This material is able to sorb bothhydrophilic and lipophilic liquids. The spent germ may be washed torender it substantially free of odor components. It is known thatwashing of the germ will remove substantially odor and flavorcomponents, which may be an advantage in some instances. In otherembodiments, unwashed germ may be used. Germ obtained from any suitablegrain may be employed in conjunction with the invention. Grains such ascorn, wheat, soy, sorghum, barley, and the like are particularlysuitable for use in conjunction with the invention. The preferredsorbent is expeller-extruded corn germ. Virgin germ (i.e., germ fromwhich oil has not been extracted) may also be used, whereby in themanufacture of the sorbent as described herein some or all oil presentin the germ is extracted.

[0018] Alternatively, or in addition thereto, the sorbent used inconjunction with the invention may be a seed meal. Examples of suchmeals include linseed meal, soybean meal, sunflower meal, cottonseedmeal, rapeseed meal, peanut meal, safflower seed meal, and combinationsthereof. By “seed” is meant to include that part of a plant which iscapable of forming a new plant upon germination, e.g., whole grains ofwheat, including the fruit or fruit-like structure housing the seed. Theseed meal comprises a spent oil bearing seed residue, which is a seedresidue from which oil has been expelled, such as by solvent extractionor expeller extraction. The extracted residue then is ground, by whichis contemplated the reduction of the residue to smaller particles,preferably to a semi-course to fine powder. It is contemplated that someseeds will include a hull that may (but need not) be removed prior toexpelling oil and grinding. Thus, the meal may comprise a dehulled meal.The seed meal in some embodiments is washed to substantially remove odorcomponents therefrom.

[0019] The germ and seed meal component of the sorbent collectivelyshould be present in the sorbent in an amount of at least 50% by drybasis weight of the sorbent. Preferably, the germ and meal are presentin a greater amount, such as an amount of 60%, 70%, 80% or 90% by weightof the sorbent. Most preferably, the germ and meal collectively arepresent in an amount of 100% by dry basis weight of the sorbent, thatis, the sorbent includes the meal and/or germ to the substantially orcomplete exclusion of other sorbents. With respect to one another, thegerm and meal can be used in any ratio desired. For instance, expressesas a percentage, the ratio may be 100% meal, 90% meal, 80% meal, 70%meal, 60% meal, 50% meal, 40% meal, 30% meal, 20% meal, 10% meal, or 0%meal (i.e., 100% germ). Other sorbents, such as these described in U.S.Pat. No. 6,391,328, optionally may be used in conjunction with thesorbents described herein, but preferably, such other sorbents are notpresent.

[0020] The sorbent may be used in conjunction with the introduction of amaterial into an environment. The environment can be any place, area, orregion in which the introduction of the material is desired. Generally,the material is selected as being desirable for use in the environment.For instance, the material may be a control agent, by which is completeda material that limits the growth of unwanted pests in the environment.A control agent preferably is selected as being an agent that limits thegrowth of the pest, by which is contemplated checking the spread of thepest by killing, sterilizing, destroying eggs or otherwise limiting thegrowth of the pest. Control agents generally are toxic chemicals; inaccordance with the invention, any control agent now known or otherwisefound to be suitable for use in limiting the growth of a pest may beused. The pest may be present in the environment, or may not be presentin the environment (in other words, it is contemplated that theenvironment may be treated prophylactically). The pest can be anyorganism whose presence in the environment is undesired. Any organismfound in the Animalia, Protista, Fungi (in particular non-mold fungi),Plantae, or Monera kingdoms may be deemed a pest in particularcircumstances, and the control agent may be any agent that limits thegrowth of such pest in the environment. With respect to animals, thepest may be mammal, for instance, a rodent such as a mouse or rat, or anon-mammal, such as a fish, bird or other animal. The invention isbelieved to be particularly applicable to the control of animals in thephylum Arthropoda, including especially the classes Insecta(representing insects, millipedes, and centipedes), and Cheliceramorpha,especially arachnids. The control agent in preferred embodiments may bea rodenticide, a herbicide, an insecticide, a fungicide, or abactericide. Specific embodiments of the invention employ, for instance,a larvicide, a pupicide, an ovicide, a hormone, a growth regulator (e.g.an insect growth regulator), a biological control agent, a microbialcontrol agent, a toxicant, a fumigant, a pheromone, a repellent, achemosterilant, a miticide, an acarcide, a molluscicide, an avicide, apredicide, an algaecide, a nematicide, an amoebicide, a nymphicide, andthe like. In preferred embodiments, the control agent is selected fromamong an animal control agent (which may be a control agent for anyspecies in the kingdom Animalia), a plant control agent (any specieswhich may be a control agent for any species in the kingdom Plantae), anon-mold fungal control agent (which may be a control agent for anyspecies in the kingdom Fungi, excepting the molds), a protist controlagent (which may be a control agent for any species in the kingdomProtista) or a monera control agent (which may be a bacterial species orany other species in the Monera kingdom). In some embodiments, thecontrol agent may be a virus control agent. Two or more agents can becombined to increase efficacy or to achieve multifunctional performancein the same composition.

[0021] Specific preferred examples of suitable control agents includeinsecticides such as temephos, chlorpyfifos, methyl isocyanate,methoprene, propaphos, DURSBAN® dimilin, malathien, carbaryl, anddiazinon; herbicides such as 2,4-D and 2,4-D ester, ammonium sulfamate,BROMACIL®, copper salts, molinate, propanil, pyrazolate, metolachlor,and the like. Other control agents include bioactives such as Bacillusthuringiensis and Bacillus sphaericus; flugicides, such as fenoxanil,iprobenfos, menopril, tricyclozole, and valdamycin, and the like. Theinvention is not limited to the foregoing, and indeed any material thatfunctions as a control agent may be used in conjunction with theinvention. U.S. Pat. Nos. 4,911,952; 4,983,390; 5997,445; 6,159,489;6,316,447; 6,335,027; and 6,340,656, all disclose numerous controlagents, any or all which in certain embodiments may be deemed suitablefor use in conjunction with the invention.

[0022] The control agent or other material sorbed within the sorbent maybe a lipophilic or oleogenous material, or may be a hydrophilic materialor a combination thereof (such as an emulsion). The material may bepresent in any amount with respect to the sorbent suitable for theintended purpose of the sorbent/material composition. In someembodiments, the material is present in an amount of at least 5% byweight of the total composition, more preferably at least 7% by weight,and even more preferably, at 10% by weight. When the sorbed material isa control agent, the sorbed material preferably is present in an amountranging from 0.001 to 50% by weight, more preferably, from 0.001 to 10%by weight, and even more preferably, from 0.005 to 5% by weight of thecomposition. In some embodiments, the sorbed material is present in anamount from 0.05 to 1%, or, within this range, from 0.05 to 0.5% byweight. More generally, any amount suitable for the intended purpose maybe employed in conjunction with the invention. The compositionoptionally may include any other additives, which may be present in anyamounts suitable for their intended purposes or omitted altogether.Examples of such additives include surfactants, spreading agents,adjuvants, other carriers, binders, deflocculating agents, dispersingagents, synergists, penetrants, suspending agents, baits,phagostimulants, sticking agents, stabilizers, coupling agents, foamingor antifoaming agents, diluents, waxes, oils, superabsorbents, and moregenerally, any other additives.

[0023] The sorbents described herein are not limited to the introductionof a control agent into an environment. To the contrary, the sorbets canbe used to introduce any desirable sorbable materials into anenvironment. It is contemplated that in some cases the sorbable materialmay be a solid material that is carried in or on the sorbent. In oneembodiment of the invention, the sorbable material is a fertilizer. Anysuitable material or synthetic fertilizer may be employed in conjunctionwith the invention. In one embodiment, the sorbable material is ananimal nutrient, such a vitamin or mineral. These materials may bepresent in any amounts suitable for their intended purpose. Theselection of specific ingredients, loading levels, and application ratesmay be made by one is skilled in the art. One embodiment of theinvention encompasses a method for fertilizing an arable area byapplying a fertilizer composition as described above. In anotherembodiment, the invention encompasses a method for providing nutrientsto an animal, the method including feeding the animal an animal nutrientcomposition as described above. The animal may be for instance, a horse,a cow, a pig, a sheep, a bird, or even a human.

[0024] The composition that includes the sorbent and sorbed material(including any additives) may be provided in any suitable form. Mostpreferably, the composition is provided in the form of discrete pluralparticles of a substantially uniform and homogenous admixture of thesorbent and the sorbed materials. In accordance with a preferredembodiment of the invention, the particles are in a form of compressedor compacted particles, i.e., in the form of granules. By “granules” ismeant particles that are compressed or compacted, such by a pelletizing,extrusion or similar compacting step. Such compression or compacting ofthe particles is preferred, inasmuch as the intraparticle cohesion ofthe particles will be enhanced by such compacting or compressing step.

[0025] The granules may be prepared via any suitable manner. Preferably,the material to be sorbed, if not a liquid, is dissolved or suspended ina liquid and the liquid is applied to the sorbent, followed bycompression of the mixture to form granules. In a highly preferredembodiment of the invention, the granules are prepared by pelletizingthe sorbent in a pellet mill. The composition may be prepared by sorbingthe material into pellets thus formed, or alternatively may be preparedby pelletizing a mixture of the material and the sorbent. In eithercase, the pellets exiting the pellet mill may be ground or crumbled tothereby reduce the granules of the composition to a desired granulesize. The mixture may be pelletized under any suitable conditions.Typically, the ingredients are pre-ground and are introduced into thepellet mill with moisture. Typical moisture content ranges from 2-30%,more preferably 5-15% by total weight of the blend. The blend ispelleted through a die such as a {fraction (3/32)} in×2 in die at anysuitable temperature, preferably a temperature ranging from 150° F. to220° F., more preferably from 180° F. to 200° F. Final moisturepreferably is in the range from 4-20%, more preferably from 7-12% bytotal weight.

[0026] After pelleting, the pellets may be cooled and crumbled throughdry rollers to reduce the size of the granules (it is also possible tocut the pellets from the die). The final granule size may vary dependingon the application. For an application such as mosquito control, thegranule size preferably should be between 4 and 30 mesh (U.S. standardtest sieve. ASTM E-11 specification) and more preferably should bebetween 6 and 20 mesh. Fines generated during the pelletizing processmay be removed by screening, preferable on a 10-mesh screen to a levelof less than 20% by weight and ideally less than 5%. Such fines may berecycled.

[0027] In the pelletizing operation, use of a lubricity agent such ascorn oil may be necessary or helpful. Other lubricants such as addedcorn oil or oils from soy, peanut, sunflower, rapeseed, canola, coconut,or cotton, or animal fats such as tallow, yellow grease, or whitegrease, may be used. Other lubricants include lecithin, waxes, fishoils, castor oil, long-chain alkyl sulphonates, alkyl poyglucosides,tall oil, stearates, and silicones. The lubricant (including any oilpresent in the germ) preferably is present in an amount of up to 30% bytotal weight of the composition (excluding moisture) more preferably, anamount of 10-15% by weight. Pelletizing is not the only manner offorming suitable granules. For instance, in another embodiment of theinvention, extrusion of sorbent through a dye and grinding of theextrudate to a suitable granular size is useful in conjunction with thepreparation of the composition. Once again, the extrudate may itselfcomprise a composition of a sorbent and the material to be sorbed, orthe material may be sorbed within granules of extruded sorbentsubsequent to extrusion.

[0028] The granules should be sufficiently cohesive for use for theirintended purpose. Especially when the granule is used as a carrier forcontrol agent, the granule must have sufficient integrity to survive theproduction, transport, and application of the product. If the granule istoo durable, however, it will not disintegrate easily, and may not beeffective in releasing the control agent in the desired manner, forinstance, when the granule is introduced into a water column. Inembodiments of the invention where a delayed release of the controlagent or other sorbed material is desired, the granules may be made moredurable by incorporating additional binder or cohesiveness agent. Thebinder may comprise an extrudate of corn hulls and sodium hydroxide (astaught is copending application Ser. No. 09/901,342, filed Jul. 9,2001), lignin, lignosulfate, hemicelluloses, celluloses, water, starchhydrolyzates, hydrogenated starch hydrolyzates, fatty acids, and claymaterials such as bentonite and zeolites. In such embodiments, thebinder preferably is present in an amount of about 5% by weight of thegranule. In some embodiments of the invention, the granules may includea polysaccharide cohesiveness agent to enhance the cohesiveness of thegranules. The cohesiveness agent is believed to provide additionalhydroxyl groups, which groups enhance the bonding between grain proteinswithin the sorbent granules. It is further believed that the additionalhydroxyl groups so function by enhancing the hydrogen bonding ofproteins to starch and to other proteins. When used, the polysaccharidecohesiveness agent may be present in any amount suitable to enhance thecohesiveness of the sorbent granules. Generally, the cohesiveness agentmay be present in a dry basis amount ranging up to about 45% by weightof the sorbent granules, preferably, an amount ranging from about 3% toabout 35% by weight, more preferably, an amount ranging from about 5% toabout 25% by weight. When the binder is or includes virgin germ, some orall of this may come from starch naturally present in the virgin germ

[0029] In accordance with these embodiments of the invention, anysuitable polysaccharide may be used in conjunction with the invention,and thus, for example, the cohesiveness agent may comprise one or morepolysaccharides such as dextrin, maltodextrins, starches, flours,cellulosics, hemicellulosics, and the like. Preferably, the cohesivenessagent comprises a starch, and most preferably, the cohesiveness agentcomprises a corn starch.

[0030] When a polysaccharide cohesiveness agent is used, preferably asupplemental cohesiveness agent also is used. In accordance with theinvention, the supplemental cohesiveness agent is an ionic species thatis believed to enhance protein-protein and/or protein-starchinteractions. Any suitable ionic salt may be used in conjunction withthe invention. For example, in accordance with preferred embodiments ofthe invention, the supplemental cohesiveness agent is selected fromamong the alkali and alkaline-earth salts of common anions, such as thehalide, nitrate, nitrite, carbonate, phosphate, sulfate, and bicarbonatesalts, and the like. More preferably, the supplemental cohesivenessagent is selected from the group consisting of sodium chloride, calciumchloride, sodium carbonate, calcium carbonate, sodium bicarbonate andmixtures thereof. Even more preferably, the supplemental cohesivenessagent is selected from among sodium chloride, calcium carbonate, andmixtures thereof. Most preferably, the supplemental cohesiveness agentis sodium chloride. The supplemental cohesiveness agent may be presentin any amount sufficient to assist the cohesiveness agent in enhancingthe cohesion of the granules. When used, the supplemental cohesivenessagent preferably is present in an amount of at least about 0.05% by drybasis weight, of the composition exclusive of the polysaccharidecohesiveness agent. More preferably, the supplemental cohesiveness agentis present in an amount ranging from about 0.05% to about 10% by weight;more preferably, about 0.1% to about 8% by weight; and most preferably,about 1.5% to about 4% by weight. In a particularly preferredembodiment, the supplemental cohesiveness agent is present in an amountof about 2% by weight of the composition.

[0031] To prevent or inhibit spoilage, the sorbent composition mayinclude a preservative. Preferably, the sorbent composition includes amold inhibitor, which may be present in any amount sufficient to inhibitthe molding of the sorbent composition. Any suitable mold inhibitor maybe employed in conjunction with the invention. The mold inhibitorpreferably is selected from among the propionate salts, and mostpreferably is selected from the group consisting of sodium propionateand calcium propionate. Other preservatives include sodiummetabisulfite, citric acid, vitamin C, vitamin E, butylatedhydroyxytoluene (BHT) butylated hydroxyanisole (BHA), and sodiumbenzoate. When a mold inhibitor is employed, it preferably is present inan amount ranging from about 0.02% to about 3.5% by weight. The moldinhibitor may function to some extent as agent for controlling mold ifthe composition is introduced into an environment; however, at thelevels used herein, the mold inhibitor is intended for the purpose ofretarding mold of the sorbent composition itself.

[0032] The composition may be introduced into an environment via anysuitable means. Where it is desired to disseminate the composition overa large area, the composition may be disseminated from an aircraft, suchas plane, helicopter, blimp, balloon, or the like, or may bedisseminated from a watercraft. Particularly when the control agent is amosquito adulticide or larvicide, the environment may be awater-containing environment, by which is contemplated any environmentcontaining standing or slowly moving water. For example, thewater-containing environment may be a pond, lake, swamp, marsh, bog,area with collected rainwater, (such as a tire) and so forth. It iscontemplated that in these or other embodiments of the invention theenvironment may be an indoor environment. The composition preferably isformulated to release at least a portion of the larvicide within thefirst two feet of water column.

[0033] The sorbent composition also may be used to remove a materialfrom an environment. In accordance with this embodiment of theinvention, at least a portion of undesired material present in anenvironment may be removed by introducing a sorbent into theenvironment, allowing the sorbent to sorb at least a portion of thematerial, and removing at least a portion of the sorbed composition fromthe environment. The material which may be removed from the environmentis not limited to the materials described herein, but to the contrary itis contemplated that any materials that is sorbable by the sorbentcomposition may be removed form an environment. For instance, thematerial may be an oleogenus or lipophilic material, or may be ahydrophilic material. In some embodiments, the material may be a gaseousmaterial, such as ammonia. Generally, the sorbent may be prepared asdescribed hereinabove, and may be introduced into the environment in anysuitable manner, for instance, by dispersing the sorbent from anaircraft or watercraft as described above. The sorbent may be introducedinto the environment in any amount effective for its intended purpose.

[0034] The sorbent used in conjunction with the invention isincinerable. It is contemplated that the sorbed material may be acombustible material, and in particular a hydrophilic material such asethanol or an oleogenous material such as oil. It is contemplated that acombustible material composition so composed may be oxidized, such as byincineration, to thereby generate heat. The heat thus generated may beused in industrial applications or may be used to generate electricalenergy. The combustible material composition may include any suitableratio of sorbent to combustible material. Preferably, the compositionincludes from 1-75%, by weight combustible material, more preferably,the combustible material is present in an amount of at least 5% byweight, even more preferably, the combustible material is present in anmount from 10-75% by weight.

[0035] The sorbents useful in conjunction with the invention arebiodegradable at 25° C. By “biodegradable” is contemplated that thesorbents are susceptible to degradation via microbial influence or otherbreakdown of the biological structure of the sorbent, such as by thermalor internal chemical or biochemical influence. It is furthercontemplated that the sorbent will be biodegradable over a wide range ofother temperatures. When the sorbent is used to introduce a materialinto an environment, in particular an outdoor environment, the sorbentpreferably is biodegradable in the environment. Such biodegradabilityprevents long-term contamination of the environment of the sorbent, and,in some embodiments, may effect a delayed release of the sorbed materialinto the environment. In embodiments of the invention where the sorbentis used to remove material from an environment, the sorbent may beallowed to biodegrade after removal of the sorbed unwanted material butbefore final disposal of the sorbed material compositions. Thebiodegradation of the sorbent will in some instances reduce the volumeof the sorbed material composition, thereby reducing the disposal costs(particularly in the case of a hazardous material). The sorbed materialmay be stored until the volume of the material has been reduced by adesired amount preferably at least 10%, more preferably 15%, and evenmore preferably 20% of the original volume.

[0036] The following Examples illustrate the invention, but should notbe construed as limiting the invention in scope.

EXAMPLE 1

[0037] Experiments were carried out to evaluate the ability of spentcorn germ to sorb various liquids. For each liquid evaluated, 15 gramsof sorbent was mixed with 10-50 grams of the liquid to be tested. After2 hours, the liquid not sorbed by the germ was drained off, and thequantity of liquid retained by the sorbent was determined. Fourcommercial products were also evaluated, two of which were claimed to beboth oil and water absorbents. The products picked up from 20 to 25% oftheir weight of water in the same period of time. The oil absorptivecapacities of the germ and the commercial products are similar.

[0038] Data below is expressed for each product as % of its weight inliquid absorbed. Germ Product A Product B Product C Water 600 (after 2hours) 26 42 32 Ethanol  72 74 74 70 Mineral oil  58 40 36 48 Dieselfuel  28 22 20 32

[0039] Product A is a silica-based commercial product.

[0040] Product B is a silica/clay-based commercial product.

[0041] Product C is a silica-based commercial product.

[0042] As seen, the germ was superior to the commercial products. Thegerm was found to sorb at least 300% of its weight of water within 5minutes, although it is believed that the ultimate capacity is evengreater over time.

EXAMPLE 2

[0043] This example demonstrates the sorption of gaseous ammonia byspent corn germ.

[0044] Sorption isotherms were conducted by treating air that contained200 ppm NH₃ with different levels of ground spent corn germ. Air testchambers each having a volume of 3717.4 cm³ were each prepared tocontain a standard mass of gaseous ammonia by placing into each chamberan open top plastic weigh boat containing 10.00 mL of a standard ammoniasolution made to contain 0.000259 g NH₃ per mL. Each test chambercontained a total of 0.00259 g NH₃, which at equilibrium would existboth as a free gas and as gas dissolved in water. Directly preceding theaddition of the ammonia solutions to the test chambers, different massesof ground spent germ of 100 g, 10 g, and 1.0 g had been added to threedifferent test chambers. Two additional test chambers were not providedwith grain germ but had only the weigh boats containing the ammoniasolution. After equilibration at 20° C. for 23 hours, the concentrationsof gaseous ammonia in the test chambers were measured with DraegerTubes.

[0045] The relationship between ppm and mg/m³ was calculated accordingto the following equation:

ppm=molar volume ×(mg/m³)÷molar mass

[0046] wherein molar volume is 24.1 liters, and molar mass is 17.0grams.

[0047] Using this calculation, a concentration of 200 ppm NH₃ represents20.23% of the total NH₃ added.

[0048] The two test chambers to which no spent germ had been added wereeach found to contain 200 ppm NH₃. Surprisingly, even the smallestamount of germ added to the chamber was sufficient to sorb gaseousammonia to a level below the level of detection. The three test chambersto which the three different amounts of ground spent germ had been addedwere each found to contain 0 ppm NH₃.

EXAMPLE 3 Preparation of Germ for Insecticide Usage

[0049] Unwashed spent corn germ (Grain Processing Corporation, 25 pounds(10% moisture) was fed into a California Pellet Mill. The conditionertemperature on the mill was 44° C. and a pellet die with 0.125×1.25 inchopenings was used. The pelleting temperature was 67-68° C. Thepelletized product was crumbled and screened across a 20-mesh screen toremove fines. The resulting product moisture was 11.5%.

EXAMPLE 4 Pelletized Germ as a Mosquito Larvicide Carrier

[0050] The pelletized germ of Example 3, 10 pounds, is imbibed with 0.2pounds of Altosid® liquid larvicide (5% active (S)-methoprene). Mixingis carried out so that an even distribution of the larvicide is achievedthroughout the pellets. The larvicide containing pellets are then usedto treat an open saltwater marsh

EXAMPLE 5 Pelletized Germ as a Mosquito Adulticide Carrier

[0051] The pelletized germ of Example 3, 10 pounds, is imbibed with 0.1pounds of Dursban® 4E liquid insecticide (44.8% active chlorpyrifos).Mixing is carried out so that an even distribution of the insecticide isachieved throughout the pellets. The insecticide containing pellets arethen used to treat an open saltwater marsh at an application rate of 0.5pounds per acre.

EXAMPLE 6

[0052] Example 4 is repeated, except that the sorbent includes graingerm, starch, and salt, which are present in a ratio of 78:20:2 withrespect to one an other.

EXAMPLE 7

[0053] Example 4 is repeated, except the sorbent includes soy meal.

EXAMPLE 8

[0054] Example 4 is repeated, except the sorbent includes soy meal,starch, and salt which are present in a ratio in 78:20:2 in respect toone another.

EXAMPLE 9

[0055] Example 4 is repeated, except the sorbent includes linseed meal.

EXAMPLE 10

[0056] Example 4 is repeated, except the sorbent includes linseed meal,starch, and salt which are present in a ratio 78:20:2 with respect toone another.

EXAMPLE 11

[0057] Example 4 is repeated, except that the sorbent is sunflower meal.

EXAMPLE 12

[0058] Example 4 is repeated, except that the sorbent is a 50:50 mixtureof spent grain germ and sunflower meal.

EXAMPLE 13

[0059] Example 4 is repeated, except that the sorbent is a 50:50 mixtureof sunflower and linseed meal.

EXAMPLE 14

[0060] U.S. Pat. No. 6,098,569 issued Aug. 8, 2002 to Kent et al. ishereby incorporated by reference in its entirety. A sorbent is preparedin accordance with “animal litter” set forth as example 2. The sorbentis used to sorb oil from a cement surface.

EXAMPLES 15-48

[0061] Ground germ, virgin germ, hexane extruted germ (HEG), corn hulls,granular starch (B200 and B700, available from Grain ProcessingCorporation of Muscatine, Iowa), Biobond E310 (a hemicellulose productavailable from Grain Processing Corporation), MALTRIN® M150 (amaltodextrin available from Grain Processing Corporation), wheatmiddlings, distearyl dimethyl ammonium chloride (TA-100), carboxymethylstarch extrduate (G120), distillers dried grains (DDG) and liquid feedsyrup (LFS) were provided and fashioned into pellets. The moisturecontent of all of the pellets was from 2%-10%. The fat (corn oil) levelof the blends ranged from 6-15%. Protein content was 20-30% of the totalblend. The formulations in the following table were prepared (thefigures in the following table are expressed as weight ratios). UnwashedVirgin Citric Weight Ratio germ germ HEG HULLS B200 B700 E310 M150 WheatMidds Acid NA₂CO₃ TA100 DDG LFS G120 Examples: 15 100 16 100 3 17 100 18100 1 19 95 5 20 95 5 5 21 90 10 10 22 90 10 10 23 90 10 20 24 90 10 525 90 10 5 26 90 10 0.1 0.2 27 90 10 28 90 10 20 29 90 10 30 90 10 31 9010 3 32 90 10 33 90 10 34 85 15 35 85 15 5 36 85 15 37 85 15 10 38 85 151 39 75 25 40 75 25 5 41 50 50 42 50 50 5 43 20 10 70 44 10 90 45 10 9010 46 10 90 47 100 48 90 10

[0062] With reference to Example 36, seventeen hundred pounds of ground,unwashed, expelled germ was blended with 300 pounds of ground virgingerm in a ribbon blender. The starting moisture of the blend was 3.9%.Water, 78 pounds, was added to the ribbon blender to bring the totalmoisture content of the blend to 7.6%. After fifteen minutes ofblending, the ground material was conveyed to a California Pellet Mill.The die size was {fraction (3/32)}″×2″. The pellets were cut-off at thedie at about ½″ in length. The feed screw setting was 8 (˜3,000lbs/hour.). The pelleting temperature was 180° F. and the mill amps were45. The steam setting to maintain temperature was 63 psi. The overallrunnability of the product was excellent and no mill amp surges wereobserved.

[0063] The pellets were conveyed from the pellet die to a cooler toallow the pellets to cool to ambient temperature. Airflow to the coolerwas minimized. The pellets were then conveyed to a dual roll crumbler,set to obtain a granule size of 35-75% through an 8-mesh screen. Thescreening consisted of a 30 seconds to one minute manual shake on an 8mesh screen, so actual granule of size was smaller than measured by thisin process technique. The crumbled pellets were then conveyed over a10-mesh screen to remove fines. The fines were recycled back to the millfor re-pelleting. The final granules were packaged in 50-pound polylined bags to prevent moisture loss.

[0064] Examples 17, 28, and 29 also were prepared in accordance with theaforementioned procedure, but with different starting blends.

[0065] With reference to Example 32, unwashed, ground, expelled germ,8.5 pounds, was blended with 1.5 pounds of ground virgin germ and 0.5pounds of B700 cornstarch. The resulting moisture of the blend was 7.9%.The blend was pelleted through a {fraction (3/32)}×⅝ inch die on aCalifornia Pellet Mill. The pellets were cut at the die so that theoptimal pellet size could be achieved. The conditioner temperature was160° F. and this temperature was maintained through the die. The feedsetting was 45 and the mill amps were 3.6.

[0066] The resulting product moisture was 11.4%.

[0067] This procedure was followed for the remainder of the blends ofExamples 15-48. (except Examples 17, 28, 29, and 36).

[0068] Granule size, durability, water disintegration; and compositionwere evaluated for several of the foregoing compositions.

[0069] A) Granule Size:

[0070] Screen profiles were obtained by weighing 100 g of granules andseparating the granules on a Tyler Ro-Tap Sieve Shaker. Shaking time was10 minutes. The screens used were U.S.A. standard sieves 8, 10, 12, 14,16 and 20 mesh. Any particles that passed through the 20-mesh screenwere considered fines. The screen profiles are listed in the followingtable. Screen Profile: % ON 8 mesh 10 mesh 12 mesh 14 mesh 16 mesh 20mesh Pan Example: 16 1.7 13.5 19.3 24.7 16.4 15.6 8.2 17 37.6 30.7 12.75.9 2.9 3.0 7.3 19 32.8 31.2 15.3 10.2 5.1 3.2 2.2 22 2.8 17.3 21.1 24.615.6 12.7 5.6 23 51.1 23.9 7.6 6.0 4.5 4.2 2.7 26 36.8 34.7 8.9 6.5 4.33.8 4.9 28 22.4 26.2 20.8 12.8 6.1 4.9 6.8 29 17.8 28.3 25.2 14.1 4.93.8 6.0 30 2.2 18.6 19.2 20.4 13.5 14.4 11.7 35 33.1 24.2 14.6 12.5 7.35.2 3.1 36 25.7 39.5 19.7 6.2 2.2 1.8 4.9 44 0.2 2.5 11.3 23.5 21.8 24.116.1 50 16.6 24.2 17.1 15.1 10.8 9.2 7.0

[0071] B) Granule Durability

[0072] Granule durability was measured by using a Ro-Tap sieve shaker. A50-gram aliquot of granules that had been previously screened to removeall fines less than 20 mesh was reapplied on a 20-mesh screen. Thegranules were then re-shaken on the Ro-Tap for 20 minutes. The fineswere measured to give an indication of how easy the granules brokeapart. Durability analyses are shown in the following table. FinesExample: g in Pan % in Pan 14 0.4 0.8 19 0.9 1.8 23 0.6 1.2 26 2.0 4.028 0.6 1.2 29 0.5 1.0 35 0.5 1.0 36 0.3 0.6

[0073] C) Granule Water Disintegration

[0074] The granule water disintegration test is a modification of theU.S. Pharmacopoeia 710 tablet disintegration test. The apparatus usedwas a VanKel® disintegration tester Vankel Industries, Edison, N.J.)which is a basket-rack assembly with six open-ended transparent tubes(7.75 cm long, 23 mm wide), of which only two tubes were used at anygiven time. The tubes are held in place by top and bottom plexiglassplates. The assembly has a woven stainless steel wire mesh (1.8-2.2 mmapertures) attached to the lower plate to allow for water to pass freelyin and out of the tubes. The assembly was suspended on a cantileverattached to a motor that consistently raises and lowers the assembly atapproximately 30 cycles per minute through a distance of 5.5 cm. A 0.25g aliquot of >20 mesh granules was placed into the individual tubes(each sample was evaluated in duplicate). The basket-rack assembly wasthen submerged into a 4L Pyrex No. 1000 beaker containing 3.5 of 27° C.tap water, and the motor turned on to initiate the movement of thebasket. The number of granules remaining in the basket was measuredafter 5, 10 and 15 minutes and the two values per sample were averaged.The granules disintegrated with time so that the majority of the pelletsbroke apart and fell through the mesh screen during the test. Thefollowing results were obtained. # of Pellets Example: Avg 5 min Avg 10min Avg 15 min 14 22 12 2 17  9  1 1 19  9  3 1 22 13  8 1 23 18  9 4 26 0 (4 min)  0 0 28  9  1 0 29  7  1 1 30  8  7 4 35  8  4 2 36  5  1 044 19 11 7 45  1  0 (6 min) 0

[0075] D) Granule Chemical Analysis

[0076] Selected granule samples were analyzed for moisture (Ohausmoisture balance), fats (ISCO SFE) and proteins (LECO nitrogenanalyzer). The following results were obtained. Example: Moisture FatsProtein 17 7.4  7.2 25.2 19 9.0  9.8 24.4 23 7.0 NR* NR 26 10.8 NR  NR28 7.3  9.7 21.6 29 7.2 10.5 23.6 35 9.0 13.2 22.4 36 6.4 12.7 23.9

[0077] For mosquito control, Example 36 is preferred.

[0078] It is thus seen that in various embodiments the foregoing generalobjects have been satisfied. The invention provides a sorbent which isuseful in conjunction with the introduction of a material into anenvironment, and in conjunction with a removal of a unwanted materialfrom an environment.

[0079] All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference.

[0080] The use of terms such as “a” and “an” and “the” and similarreferents in the context of describing the invention is to be construedto cover both the singular and the plural, unless other wise indicatedherein or clearly contradicted by context. All methods described hereincan be preformed in any suitable order unless otherwise indicated hereinor otherwise clearly contradicted by context. The use of any and allexamples, or exemplary language provided herein, is intended toilluminate the invention and does not pose a limitation on the scope ofthe invention. No language in the specification should be construed asindicating any non-claimed element as being essential to the practice ofthe invention. Preferred embodiments of this invention are describedherein. Variations of those preferred embodiments may become apparent tothose of ordinary skill in the art upon reading the foregoingdescription. Accordingly, this invention includes all modifications andequivalents of the subject matter recited in the claims appended heretoas permitted by applicable law.

What is claimed is:
 1. A composition comprising: a sorbent, said sorbentbeing selected from the group consisting of spent grain germ, seed meal,and mixtures thereof; and a control agent sorbed within said sorbent,said control agent being selected from the group consisting of an animalcontrol agent, a plant control agent, a non-mold fungal control agent, aprotist control agent, and a monera control agent.
 2. A compositionaccording to claim 1, said sorbent including spent corn germ.
 3. Acomposition according to claim 1, said control agent being present in anamount of 0.001 to 50% by weight of said composition.
 4. A compositionaccording to claim 3, said control agent being present in an amount of0.001 to 10% by weight of said composition.
 5. A composition accordingto claim 1, said composition being in the form of discrete pluralpellets.
 6. A composition according to claim 5, said control agentcomprising a mosquito larvicide.
 7. A method for limiting the growth ofan undesired pest in an environment, the method comprising: selecting acontrol agent for said pest; introducing into said environment an amountof a control agent composition effective to limit the growth of saidpest, said control agent composition comprising; a sorbent, said sorbentbeing selected from the group consisting of spent grain germ, seed meal,and mixtures thereof; a control agent sorbed within said sorbent, saidcontrol agent being effective to limit the growth of said pest.
 8. Amethod according to claim 7, said sorbent including spent corn germ. 9.A method according to claim 7, said control agent being present in anamount of 0.001 to 50% by weight of said composition.
 10. A methodaccording to claim 9, said control agent being present in an amount of0.10 to 10% by weight of said composition.
 11. A method according toclaim 7, said composition being in the form of discrete plural pellets.12. A method according to claim 8, said control agent being a mosquitolarvicide.
 13. A method according to claim 7, the method including thestep of introducing said composition into said environment by dispersingsaid composition from an aircraft.
 14. A method for removing an unwantedmaterial present in an environment from said environment, comprising;selecting a sorbent for said material, said material being sorbablewithin said sorbent, said sorbent being selected from the groupconsisting of spent grain germ, seed meal, and mixtures thereof;introducing into said environment an amount of said sorbent effective tosorb at least a portion of said material; allowing at least some of saidmaterial to become sorbed within said sorbent to thereby form a sorbedcomposition; and removing at least a portion of the sorbed compositionfrom said environment.
 15. A method according to claim 14, said sorbentincluding washed, spent corn germ.
 16. A method according to claim 14,said sorbent being introduced into said environment by dispersing saidsorbent from an aircraft.
 17. A method according to claim 14, saidmaterial being a gas.
 18. A method according to claim 14, said materialcomprising an oleogenous material.
 19. A method according to claim 18,said material comprising a combustible material.
 20. A method accordingto claim 14, further comprising: after removing said sorbed compositionfrom said environment, allowing said sorbed composition to biodegrade tothereby form a biodegraded sorbed material, said sorbed compositionbeing allowed to biodegrade to an extent such that the volume of saidbiodegraded sorbed composition is no more than 90% of the volume of saidsorbed composition prior to biodegradation
 21. A method for generatingheat, comprising, providing a combustible material composition, saidcombustible material composition comprising: a sorbent, said sorbentbeing selected from the group consisting of spent grain germ, seed mealand mixtures thereof, and a combustible material sorbed within saidsorbent; and oxidizing said combustible material composition.
 22. Amethod according to claim 21, said sorbent including spent corn germ.23. A method according to claim 21, said combustible material beingpresent in an amount of 1 to 75% by weight of said composition.
 24. Amethod according to claim 21, said combustible material being anoleogenus material.
 25. A combustible material composition comprising asorbent, said sorbent being selected from the group consisting of spentgrain germ, seed meal and mixtures thereof, and a combustible materialsorbed within said sorbent and present in an amount of at least 5% byweight of said composition.
 26. A composition according to claim 25,said sorbent including spent corn germ.
 27. A composition according toclaim 25, said combustible material being present in an amount of 10 to75% by weight of said composition.
 28. A composition according to claim25, said combustible material being oleogenous.
 29. A method forintroducing a material into an environment, comprising: selecting amaterial for which delayed release of said material into saidenvironment is desirable; introducing into said environment a materialcomposition, said composition including said material sorbed within asorbent, said sorbent being selected from the group consisting of spentgrain germ, seed meal, and mixtures thereof, said material being presentwith respect to said sorbent in an amount effective to release at leasta portion of said material upon biodegradation of said sorbent, saidsorbent being biodegradable in said environment.
 30. A method accordingto claim 29, said material being an oleogenous material.
 31. A methodaccording to claim 29, said sorbent including spent corn germ.
 32. Amethod according to claim 29, said material being present in an amountof 1 to 75% by weight of said composition.
 33. A method according toclaim 32, said material being present in an amount of 10 to 75% byweight of said composition.
 34. A method according to claim 29, saidcomposition being in the form of discrete plural pellets.
 35. A methodaccording to claim 29, the method including the step of introducing saidmaterial into said environment by dispersing said material compositionfrom an aircraft.
 36. A fertilizer composition comprising: a sorbent,said sorbent being selected from the group consisting of spent graingerm, seed meal, and mixture thereof; and a fertilizer sorbed withinsaid sorbent.
 37. A method for fertilizing an arable land area,comprising applying the fertilizer composition of claim
 36. 38. Ananimal feed composition comprising; a sorbent, said sorbent beingselected from group consisting of spent grain germ, seed meal, andmixtures thereof; and an animal nutrient sorbed within said sorbent. 39.A method for providing nutrients to an animal, comprising; feeding theanimal the animal feed composition of claim 38.